Abstract: Poly(vinyl alcohol) (PVA) nanofibers were prepared by an electrospinning technology, and their process parameters such as spinning voltage, spinning distance and spinning solution concentration were adjusted by an orthogonal experiment. The effect of these process parameters on the diameter and its distribution and morphology of PVA nanofibers was also investigated. The results indicated that the main influence factors for fiber morphology followed an order of spinning solution concentration>spinning distance>spinning voltage. An optimum combination of process parameters was determined as a spinning voltage of 20 kV, a spinning solution concentration of 6 wt % and a spinning distance of 12 cm.